CA2885137A1 - Electrically conductive polyamide moulding materials - Google Patents
Electrically conductive polyamide moulding materials Download PDFInfo
- Publication number
- CA2885137A1 CA2885137A1 CA2885137A CA2885137A CA2885137A1 CA 2885137 A1 CA2885137 A1 CA 2885137A1 CA 2885137 A CA2885137 A CA 2885137A CA 2885137 A CA2885137 A CA 2885137A CA 2885137 A1 CA2885137 A1 CA 2885137A1
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- CA
- Canada
- Prior art keywords
- weight
- moulding material
- polyamide
- polyamide moulding
- material according
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 239000000463 material Substances 0.000 title claims abstract description 85
- 239000004952 Polyamide Substances 0.000 title claims abstract description 79
- 238000000465 moulding Methods 0.000 title claims abstract description 75
- 229920002647 polyamide Polymers 0.000 title claims abstract description 72
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 52
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 45
- 239000000203 mixture Substances 0.000 claims abstract description 36
- 229920006125 amorphous polymer Polymers 0.000 claims abstract description 21
- 239000000835 fiber Substances 0.000 claims abstract description 21
- 239000006229 carbon black Substances 0.000 claims abstract description 18
- 239000000654 additive Substances 0.000 claims abstract description 16
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 16
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 13
- 239000011707 mineral Substances 0.000 claims abstract description 13
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 12
- 239000011780 sodium chloride Substances 0.000 claims abstract description 12
- 229920006114 semi-crystalline semi-aromatic polyamide Polymers 0.000 claims abstract description 11
- 230000000996 additive effect Effects 0.000 claims abstract description 8
- 230000009477 glass transition Effects 0.000 claims abstract description 7
- 229920001955 polyphenylene ether Polymers 0.000 claims description 29
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 26
- 239000000945 filler Substances 0.000 claims description 18
- -1 PA 1212 Polymers 0.000 claims description 17
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 14
- 229920006119 nylon 10T Polymers 0.000 claims description 14
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 12
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 12
- 229920006111 poly(hexamethylene terephthalamide) Polymers 0.000 claims description 12
- 239000004609 Impact Modifier Substances 0.000 claims description 9
- 229920000572 Nylon 6/12 Polymers 0.000 claims description 9
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 8
- 229920006131 poly(hexamethylene isophthalamide-co-terephthalamide) Polymers 0.000 claims description 8
- 235000012211 aluminium silicate Nutrition 0.000 claims description 7
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 7
- 239000003381 stabilizer Substances 0.000 claims description 7
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 5
- 239000000314 lubricant Substances 0.000 claims description 5
- QQOMQLYQAXGHSU-UHFFFAOYSA-N 2,3,6-Trimethylphenol Chemical compound CC1=CC=C(C)C(O)=C1C QQOMQLYQAXGHSU-UHFFFAOYSA-N 0.000 claims description 4
- 239000005995 Aluminium silicate Substances 0.000 claims description 4
- 229920006153 PA4T Polymers 0.000 claims description 4
- 239000006096 absorbing agent Substances 0.000 claims description 4
- 239000004927 clay Substances 0.000 claims description 4
- 238000002425 crystallisation Methods 0.000 claims description 4
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 4
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 3
- 239000010445 mica Substances 0.000 claims description 3
- 229910052618 mica group Inorganic materials 0.000 claims description 3
- 239000000454 talc Substances 0.000 claims description 3
- 229910052623 talc Inorganic materials 0.000 claims description 3
- 235000012222 talc Nutrition 0.000 claims description 3
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims description 2
- 239000004150 EU approved colour Substances 0.000 claims description 2
- 239000004608 Heat Stabiliser Substances 0.000 claims description 2
- 229920000305 Nylon 6,10 Polymers 0.000 claims description 2
- 229920006152 PA1010 Polymers 0.000 claims description 2
- 230000004913 activation Effects 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 239000000956 alloy Substances 0.000 claims description 2
- 229910045601 alloy Inorganic materials 0.000 claims description 2
- 239000002216 antistatic agent Substances 0.000 claims description 2
- 239000010428 baryte Substances 0.000 claims description 2
- 229910052601 baryte Inorganic materials 0.000 claims description 2
- 239000002981 blocking agent Substances 0.000 claims description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 2
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- 235000012241 calcium silicate Nutrition 0.000 claims description 2
- 239000001175 calcium sulphate Substances 0.000 claims description 2
- 235000011132 calcium sulphate Nutrition 0.000 claims description 2
- 238000004132 cross linking Methods 0.000 claims description 2
- 239000003431 cross linking reagent Substances 0.000 claims description 2
- 239000003814 drug Substances 0.000 claims description 2
- 230000005611 electricity Effects 0.000 claims description 2
- 238000005516 engineering process Methods 0.000 claims description 2
- 239000003063 flame retardant Substances 0.000 claims description 2
- 230000007062 hydrolysis Effects 0.000 claims description 2
- 238000006460 hydrolysis reaction Methods 0.000 claims description 2
- 239000001023 inorganic pigment Substances 0.000 claims description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 2
- 239000001095 magnesium carbonate Substances 0.000 claims description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 2
- 239000000347 magnesium hydroxide Substances 0.000 claims description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 2
- 238000011089 mechanical engineering Methods 0.000 claims description 2
- 239000002667 nucleating agent Substances 0.000 claims description 2
- 229940006093 opthalmologic coloring agent diagnostic Drugs 0.000 claims description 2
- 230000003287 optical effect Effects 0.000 claims description 2
- 239000012860 organic pigment Substances 0.000 claims description 2
- 229920006115 poly(dodecamethylene terephthalamide) Polymers 0.000 claims description 2
- 229920006139 poly(hexamethylene adipamide-co-hexamethylene terephthalamide) Polymers 0.000 claims description 2
- 229920006181 poly(hexamethylene terephthalamide)-co-poly(hexamethylene dodecanediamide) Polymers 0.000 claims description 2
- 229920006128 poly(nonamethylene terephthalamide) Polymers 0.000 claims description 2
- 229920006012 semi-aromatic polyamide Polymers 0.000 claims description 2
- 150000004760 silicates Chemical class 0.000 claims description 2
- 239000000306 component Substances 0.000 claims 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims 1
- 239000011521 glass Substances 0.000 claims 1
- 230000005226 mechanical processes and functions Effects 0.000 claims 1
- 229910021653 sulphate ion Inorganic materials 0.000 claims 1
- 235000019241 carbon black Nutrition 0.000 description 15
- 229940105289 carbon black Drugs 0.000 description 14
- 229920001577 copolymer Polymers 0.000 description 10
- 229910021393 carbon nanotube Inorganic materials 0.000 description 6
- 239000002041 carbon nanotube Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000013329 compounding Methods 0.000 description 6
- 229920006020 amorphous polyamide Polymers 0.000 description 5
- 239000008187 granular material Substances 0.000 description 5
- 238000010137 moulding (plastic) Methods 0.000 description 5
- 229920006060 Grivory® Polymers 0.000 description 4
- 239000011231 conductive filler Substances 0.000 description 4
- 239000003607 modifier Substances 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- 229920000265 Polyparaphenylene Polymers 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000012764 mineral filler Substances 0.000 description 3
- 238000010422 painting Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- MEMNKNZDROKJHP-UHFFFAOYSA-M 1-butyl-3-methylimidazol-3-ium;methyl sulfate Chemical compound COS([O-])(=O)=O.CCCCN1C=C[N+](C)=C1 MEMNKNZDROKJHP-UHFFFAOYSA-M 0.000 description 2
- 229920003317 Fusabond® Polymers 0.000 description 2
- 239000004961 Radipol Substances 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- DHNCFAWJNPJGHS-UHFFFAOYSA-J [C+4].[O-]C([O-])=O.[O-]C([O-])=O Chemical compound [C+4].[O-]C([O-])=O.[O-]C([O-])=O DHNCFAWJNPJGHS-UHFFFAOYSA-J 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- 239000003273 ketjen black Substances 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920006123 polyhexamethylene isophthalamide Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004953 Aliphatic polyamide Substances 0.000 description 1
- 229920002943 EPDM rubber Polymers 0.000 description 1
- 229920003314 Elvaloy® Polymers 0.000 description 1
- 229920002430 Fibre-reinforced plastic Polymers 0.000 description 1
- OKOBUGCCXMIKDM-UHFFFAOYSA-N Irganox 1098 Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)NCCCCCCNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 OKOBUGCCXMIKDM-UHFFFAOYSA-N 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- 239000004918 carbon fiber reinforced polymer Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011151 fibre-reinforced plastic Substances 0.000 description 1
- 239000000727 fraction Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229920006017 homo-polyamide Polymers 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 229940044600 maleic anhydride Drugs 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000007591 painting process Methods 0.000 description 1
- 229920000412 polyarylene Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229920006345 thermoplastic polyamide Polymers 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/14—Conductive material dispersed in non-conductive inorganic material
- H01B1/18—Conductive material dispersed in non-conductive inorganic material the conductive material comprising carbon-silicon compounds, carbon or silicon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/06—Elements
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08L71/12—Polyphenylene oxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/001—Conductive additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/06—Polymer mixtures characterised by other features having improved processability or containing aids for moulding methods
Abstract
A polyamide moulding material with the following composition is proposed: (a) 20 to 85% by weight of at least one semi-crystalline polyamide; (b) 4 to 18% by weight of carbon fibres with a fibre diameter in the range of 2 to 10 µm; (c) 10 to 60% by weight of at least one particulate mineral or saline fill- er; (d) 3 to 30% by weight of at least one amorphous polymer with a glass transition temperature of at least 45°C determined according to ISO 11357; (e) 0 to 20% by weight of carbon black; (f) 0 to 20% by weight of at least one further additive and/or addition agent; wherein the components (a) to (f) add up in total to 100% by weight.
Description
Electrically conductive polyamide moulding materials The present invention relates to electrically conductive polyamide moulding ma-terials, moulded bodies made from said moulding materials, and the use of par-ticulate fillers for increasing the electrical conductivity of polyamide moulding materials containing carbon fibres.
In addition to their good thermal and electric conductivity, carbon fibres are es-pecially characterized by their low weight. Carbon fibres usually have a diame-ter in the range of 2 to 10 pm and are mostly produced on the basis of polyac-rylonitrile (PAN). Carbon fibre reinforced plastic materials (also known under the abbreviation CFRP) are used in lightweight construction in aviation and astro-nautics or for sports appliances for example due to the aforementioned low weight and their outstanding mechanical properties.
As a result of their good electrical conductivity, CFRPs are suitable among other things for applications in which antistatic properties play a role. CFRPs can also be used advantageously in electrostatic painting. In the latter application, high demands are also placed on the surface quality of the moulded parts. As a re-sult of the high price of carbon fibres, there is a desire to reach the electrostatic conductivity required for the respective application with the lowest possible frac-tion of carbon fibres.
It is the object of WO 2010/128013 Al to provide electrically conductive poly-amide moulding materials whose electric conductivity is virtually independent of absorption of water. A moulding material of a thermoplastic polyamide, a polymerizate of propylene, a special compatibilizer and a conductivity additive from the range of carbon fibres and carbon nanotubes are disclosed as the solu-tion for the object of the invention. It is the object of the polymerizate of pro-
In addition to their good thermal and electric conductivity, carbon fibres are es-pecially characterized by their low weight. Carbon fibres usually have a diame-ter in the range of 2 to 10 pm and are mostly produced on the basis of polyac-rylonitrile (PAN). Carbon fibre reinforced plastic materials (also known under the abbreviation CFRP) are used in lightweight construction in aviation and astro-nautics or for sports appliances for example due to the aforementioned low weight and their outstanding mechanical properties.
As a result of their good electrical conductivity, CFRPs are suitable among other things for applications in which antistatic properties play a role. CFRPs can also be used advantageously in electrostatic painting. In the latter application, high demands are also placed on the surface quality of the moulded parts. As a re-sult of the high price of carbon fibres, there is a desire to reach the electrostatic conductivity required for the respective application with the lowest possible frac-tion of carbon fibres.
It is the object of WO 2010/128013 Al to provide electrically conductive poly-amide moulding materials whose electric conductivity is virtually independent of absorption of water. A moulding material of a thermoplastic polyamide, a polymerizate of propylene, a special compatibilizer and a conductivity additive from the range of carbon fibres and carbon nanotubes are disclosed as the solu-tion for the object of the invention. It is the object of the polymerizate of pro-
- 2 -pylene to reduce the absorption of water of the moulding material. The compat-ibilizer produces the compatibility between polyolefin and polyamide.
US 2003/0134963 Al relates to an electrically conductive resin composition, which comprises a polyamide, a polyphenylene ether (PPE), an impact modifier and an electrically conductive filler. Conductive carbon black, carbon nanotubes and carbon nanofibres are disclosed as electrically conductive fillers. Carbon nanotubes are processed in the examples in addition to a special conductive carbon black.
US 2006/0124906 Al discloses a composition based on polyamide which com-prises electrically conductive fillers. These moulding materials are suitable among other things for electrostatic painting processes. Carbon fibres are dis-closed among other things as electrically conductive fillers. A special conductive carbon black is used in the examples.
EP 0 877 049 Al describes an electrostatically coated polyamide material. A
composition is disclosed for the polyamide material which contains 25-90% by weight of polyamide, 5-50% by weight of a mineral filler and 0.1-25% by weight of carbon black and/or carbon fibre. The addition of the mineral filler en-sures a constant charge distribution in the material, leading to an improved, more constant adhesion of the paint. In addition to the preferred spherical ce-ramic material, Kaolin, calcium carbonate, calcium and barium sulphate as well as clay and mica are proposed as mineral fillers, among others.
EP 2 463 341 Al describes an electrically conductive plastic moulding material which contains a polyamide, a polyphenylene ether and a fine carbon fibre. The moulding material can contain additional components such as barium sulphate, calcium carbonate, clay minerals, talcum etc. The fine carbon fibres described herein do not concern cylindrical structures, but agglomerates of temple-bell-shaped carbon crystals with overlapping lattice planes, which crystals are
US 2003/0134963 Al relates to an electrically conductive resin composition, which comprises a polyamide, a polyphenylene ether (PPE), an impact modifier and an electrically conductive filler. Conductive carbon black, carbon nanotubes and carbon nanofibres are disclosed as electrically conductive fillers. Carbon nanotubes are processed in the examples in addition to a special conductive carbon black.
US 2006/0124906 Al discloses a composition based on polyamide which com-prises electrically conductive fillers. These moulding materials are suitable among other things for electrostatic painting processes. Carbon fibres are dis-closed among other things as electrically conductive fillers. A special conductive carbon black is used in the examples.
EP 0 877 049 Al describes an electrostatically coated polyamide material. A
composition is disclosed for the polyamide material which contains 25-90% by weight of polyamide, 5-50% by weight of a mineral filler and 0.1-25% by weight of carbon black and/or carbon fibre. The addition of the mineral filler en-sures a constant charge distribution in the material, leading to an improved, more constant adhesion of the paint. In addition to the preferred spherical ce-ramic material, Kaolin, calcium carbonate, calcium and barium sulphate as well as clay and mica are proposed as mineral fillers, among others.
EP 2 463 341 Al describes an electrically conductive plastic moulding material which contains a polyamide, a polyphenylene ether and a fine carbon fibre. The moulding material can contain additional components such as barium sulphate, calcium carbonate, clay minerals, talcum etc. The fine carbon fibres described herein do not concern cylindrical structures, but agglomerates of temple-bell-shaped carbon crystals with overlapping lattice planes, which crystals are
- 3 -stacked on top of each other in the axial direction. The conductivity mechanism of this longitudinally agglomerated crystal structure cannot be compared to oth-er carbon fibrils or regular carbon fibres, but the electrical conduction occurs via the surface and the tunnel effect in the region of the overlapping ends. The fine carbon fibres with the special structure of EP 2 463 341 Al have an outside di-ameter of 5 to 40 nm.
US 2006/0122310 Al describes conductive polyarylene polyamide blends, which are suitable for electrostatic painting and show a high surface quality. Clay to-gether with Kaolin and aluminium silicates are preferred additives. The conduc-tivity agents are selected from carbon black and/or carbon fibrils. These carbon fibrils concern carbon nanotubes with an outside diameter of up to 75 nm.
Their share in the mass is 0.1 to 3% by weight.
WO 01/36536 Al concerns conductive polyphenylene ether polyamide blends with carbon fibrils. The same carbon fibrils (carbon nanotubes) as in US 2006/
0122310 Al are used, and Hyperion is also mentioned as the source. The con-tent of the carbon fibrils in the moulding material is indicated with 0.4 to 3.0%
by weight (percent by weight).
It is the object of the present invention to provide carbon-fibre reinforced poly-amide moulding materials with a carbon fibre diameter in the usual range, which show high electrical conductivity respectively low electrical resistance. It is a further object of the invention to provide polyamide moulding materials from which polyamide moulded bodies with smooth surface (high gloss) can be produced. Furthermore, moulded bodies from the moulding materials in accord-ance with the invention shall have very good mechanical properties.
This object is achieved in accordance with the present invention by a polyamide moulding material with the following composition:
(a) 20 to 85% by weight of at least one semi-crystalline polyamide;
,
US 2006/0122310 Al describes conductive polyarylene polyamide blends, which are suitable for electrostatic painting and show a high surface quality. Clay to-gether with Kaolin and aluminium silicates are preferred additives. The conduc-tivity agents are selected from carbon black and/or carbon fibrils. These carbon fibrils concern carbon nanotubes with an outside diameter of up to 75 nm.
Their share in the mass is 0.1 to 3% by weight.
WO 01/36536 Al concerns conductive polyphenylene ether polyamide blends with carbon fibrils. The same carbon fibrils (carbon nanotubes) as in US 2006/
0122310 Al are used, and Hyperion is also mentioned as the source. The con-tent of the carbon fibrils in the moulding material is indicated with 0.4 to 3.0%
by weight (percent by weight).
It is the object of the present invention to provide carbon-fibre reinforced poly-amide moulding materials with a carbon fibre diameter in the usual range, which show high electrical conductivity respectively low electrical resistance. It is a further object of the invention to provide polyamide moulding materials from which polyamide moulded bodies with smooth surface (high gloss) can be produced. Furthermore, moulded bodies from the moulding materials in accord-ance with the invention shall have very good mechanical properties.
This object is achieved in accordance with the present invention by a polyamide moulding material with the following composition:
(a) 20 to 85% by weight of at least one semi-crystalline polyamide;
,
- 4 -(b) 4 to 18% by weight of carbon fibres with a fibre diameter in the range of 2 to 10 pm, (c) 10 to 60% by weight of at least one particulate mineral or saline filler;
(d) 3 to 30% by weight of at least one amorphous polymer with a glass transition temperature of at least 45 C determined according to ISO
11357;
(e) 0 to 20% by weight of carbon black;
(f) 0 to 20% by weight of at least one further additive and/or addition agent, wherein the components (a) to (f) add up in total to 100% by weight.
Preferred embodiments of the polyamide moulding material in accordance with the invention are provided in the dependent claims. Polyamide moulded bodies are further claimed, which consist at least in sections of a polyamide moulding material in accordance with the invention. The use of particulate mineral or sa-line fillers in carbon-fibre-containing polyamide moulding materials is further claimed.
Notice shall be taken at this point that the term "polyamide" (abbreviated PA) is a generic term which comprises homopolyamides and copolyamides as well as mixtures thereof. The notations and abbreviations for polyamides and their monomers are determined in the ISO standard 1874-1:1992(E).
The at least one semi-crystalline polyamide (a) is preferably an aliphatic, espe-cially a linear-aliphatic, or a semi-aromatic polyamide.
Especially preferred semi-crystalline polyamides (a) are selected from the group consisting of PA 46, PA 6, PA 66, PA 11, PA 12, PA 610, PA 1212, PA 1010, PA
10/11, PA 10/12, PA 11/12, PA 6/10, PA 6/12, PA 6/9, PA 8/10, PA 612, PA
614, PA 66/6, PA 4T/4I, PA 4T/6I, PA 5T/5I, PA 6T/6I, PA 6T/6I/6, PA 6T/66, PA
6T/610, PA 10T/106, PA 6T/612, PA 6T/10T, PA 6T/10I, PA 9T, PA 10T, PA 12T, , CA 02885137 2015-03-13
(d) 3 to 30% by weight of at least one amorphous polymer with a glass transition temperature of at least 45 C determined according to ISO
11357;
(e) 0 to 20% by weight of carbon black;
(f) 0 to 20% by weight of at least one further additive and/or addition agent, wherein the components (a) to (f) add up in total to 100% by weight.
Preferred embodiments of the polyamide moulding material in accordance with the invention are provided in the dependent claims. Polyamide moulded bodies are further claimed, which consist at least in sections of a polyamide moulding material in accordance with the invention. The use of particulate mineral or sa-line fillers in carbon-fibre-containing polyamide moulding materials is further claimed.
Notice shall be taken at this point that the term "polyamide" (abbreviated PA) is a generic term which comprises homopolyamides and copolyamides as well as mixtures thereof. The notations and abbreviations for polyamides and their monomers are determined in the ISO standard 1874-1:1992(E).
The at least one semi-crystalline polyamide (a) is preferably an aliphatic, espe-cially a linear-aliphatic, or a semi-aromatic polyamide.
Especially preferred semi-crystalline polyamides (a) are selected from the group consisting of PA 46, PA 6, PA 66, PA 11, PA 12, PA 610, PA 1212, PA 1010, PA
10/11, PA 10/12, PA 11/12, PA 6/10, PA 6/12, PA 6/9, PA 8/10, PA 612, PA
614, PA 66/6, PA 4T/4I, PA 4T/6I, PA 5T/5I, PA 6T/6I, PA 6T/6I/6, PA 6T/66, PA
6T/610, PA 10T/106, PA 6T/612, PA 6T/10T, PA 6T/10I, PA 9T, PA 10T, PA 12T, , CA 02885137 2015-03-13
- 5 -PA 10T/10I, PA10T/12, PA10T/11, PA 6T/9T, PA 6T/12T, PA 6T/10T/6I, PA
6T/6I/6, PA 6T/6I/12, PA 10T/612, PA 10T/610, and/or mixtures, blends or alloys of said polyamides, wherein PA 66 and PA 612 are especially preferred.
In a preferred embodiment, the at least one semi-crystalline polyamide (a) is contained in the polyamide moulding material with 25 to 50% by weight, espe-cially preferably 27 to 45% by weight, and more preferably 30 to 40% by weight.
The polyamide moulding material in accordance with the invention contains 4 to 18% by weight and preferably 5 to 16% by weight of carbon fibres (b).
If higher quantities of the carbon fibres are used, the moulding material be-comes very expensive and the surface quality can additionally deteriorate. Fur-therrnore, materials become brittle at higher carbon fibre fractions without fur-ther improving the electrical properties. In the case of lower quantities of car-bon fibres however, the electrical and mechanical properties of the moulding material will become poor.
Furthermore, a polyamide moulding material in accordance with the invention is preferred if the employed carbon fibres (b) have an average length in the range of between 100 and 15000 pm. After compounding, the fibre length in the granulate is usually between 100 and 500 pm and usually between 100 and 400 pm in the completed component. If pultrusion methods are applied, the fibre length in the granulate corresponds to the length of the granulate. The diameter of the carbon fibres lies in the range of 2 to 10 pm and preferably in the range of 3 to 9 pm. The carbon fibres (b) preferably have a cylindrical shape.
It is possible to use both coated and also uncoated carbon fibres. It is possible to use a single type of carbon fibres or also mixtures of two or more types of carbon fibres.
, ,
6T/6I/6, PA 6T/6I/12, PA 10T/612, PA 10T/610, and/or mixtures, blends or alloys of said polyamides, wherein PA 66 and PA 612 are especially preferred.
In a preferred embodiment, the at least one semi-crystalline polyamide (a) is contained in the polyamide moulding material with 25 to 50% by weight, espe-cially preferably 27 to 45% by weight, and more preferably 30 to 40% by weight.
The polyamide moulding material in accordance with the invention contains 4 to 18% by weight and preferably 5 to 16% by weight of carbon fibres (b).
If higher quantities of the carbon fibres are used, the moulding material be-comes very expensive and the surface quality can additionally deteriorate. Fur-therrnore, materials become brittle at higher carbon fibre fractions without fur-ther improving the electrical properties. In the case of lower quantities of car-bon fibres however, the electrical and mechanical properties of the moulding material will become poor.
Furthermore, a polyamide moulding material in accordance with the invention is preferred if the employed carbon fibres (b) have an average length in the range of between 100 and 15000 pm. After compounding, the fibre length in the granulate is usually between 100 and 500 pm and usually between 100 and 400 pm in the completed component. If pultrusion methods are applied, the fibre length in the granulate corresponds to the length of the granulate. The diameter of the carbon fibres lies in the range of 2 to 10 pm and preferably in the range of 3 to 9 pm. The carbon fibres (b) preferably have a cylindrical shape.
It is possible to use both coated and also uncoated carbon fibres. It is possible to use a single type of carbon fibres or also mixtures of two or more types of carbon fibres.
, ,
- 6 -In a special embodiment, the polyamide moulding material is completely free from fibrous reinforcing materials other than the carbon fibres.
The particulate mineral or saline fillers (c) are preferably selected from the group consisting of calcium carbonate, magnesium carbonate, dolomite, calcium hydroxide, magnesium hydroxide, calcium sulphate, barium sulphate, barite, calcium silicates, aluminium silicates, kaolin, chalk, mica, layered silicates, tal-cum, clay, and/or mixtures of said fillers, wherein calcium carbonate is especial-ly preferred.
The average diameter of the particulate mineral or saline fillers (c) usually lies in the range of 0.01 to 100 pm, preferably in the range of 0.05 to 25 pm, and especially preferably in the range of 0.06 to 5 pm.
The particulate mineral or saline fillers (c) can also have an influence on the surface gloss of the moulded bodies produced from the polyamide moulding ma-terial in accordance with the invention, depending on the structure or particle size.
The particulate mineral or saline filler (c) is preferably contained in the polyam-ide moulding material with 15 to 55% by weight, especially preferably with 20 to 50% by weight, and more preferably with 35 to 45% by weight. If higher quantities of the filler (c) are used, the mechanical properties of the moulding material will become poor and respective moulded parts will become very brit-tle. In the case of lower quantities however, the electrical properties of the moulding material will deteriorate.
The at least one amorphous polymer (d) is preferably selected from the group consisting of amorphous polyamides and polyphenylene ethers.
The particulate mineral or saline fillers (c) are preferably selected from the group consisting of calcium carbonate, magnesium carbonate, dolomite, calcium hydroxide, magnesium hydroxide, calcium sulphate, barium sulphate, barite, calcium silicates, aluminium silicates, kaolin, chalk, mica, layered silicates, tal-cum, clay, and/or mixtures of said fillers, wherein calcium carbonate is especial-ly preferred.
The average diameter of the particulate mineral or saline fillers (c) usually lies in the range of 0.01 to 100 pm, preferably in the range of 0.05 to 25 pm, and especially preferably in the range of 0.06 to 5 pm.
The particulate mineral or saline fillers (c) can also have an influence on the surface gloss of the moulded bodies produced from the polyamide moulding ma-terial in accordance with the invention, depending on the structure or particle size.
The particulate mineral or saline filler (c) is preferably contained in the polyam-ide moulding material with 15 to 55% by weight, especially preferably with 20 to 50% by weight, and more preferably with 35 to 45% by weight. If higher quantities of the filler (c) are used, the mechanical properties of the moulding material will become poor and respective moulded parts will become very brit-tle. In the case of lower quantities however, the electrical properties of the moulding material will deteriorate.
The at least one amorphous polymer (d) is preferably selected from the group consisting of amorphous polyamides and polyphenylene ethers.
- 7 -The at least one amorphous polymer (d) is especially preferably selected from the group consisting of PA 61, PA 101, copolyamides 6I/6T with a mol ratio of isophthalic acid to terephthalic acid of between 1:0 and 3:2, copolyamides 10I/10T with a mol ratio of isophthalic acid to terephthalic acid of between 1:0 and 3:2, polyphenylene ethers, especially poly(2,6-diethy1-1,4-phenylene) ether, poly(2-methy1-6-ethy1-1,4-phenylene) ether, poly(2-methy1-6-propyl-1,4-phenylene) ether, poly(2,6-dipropy1-1,4-phenylene) ether, poly(2-ethy1-6-propy1-1,4-phenylene) ether, polyphenylene ether copolymers which contain 2,3,6-trimethyl phenol, grafted variants (preferably grafted with maleic anhy-dride, abbreviated MAH) of the aforementioned polyphenylene ethers, and fur-ther mixtures of the aforementioned polyphenylene ethers, and/or mixtures of the aforementioned amorphous polymers, wherein a copolyamide 6I/6T with a mol ratio of isophthalic acid to terephthalic acid of 2:1 is especially preferred.
The expression "mixtures" in connection with the component (d) means that in such a case two or more amorphous polymers (d) are contained in the polyam-ide moulding material in accordance with the invention. They can be added sep-arately to a compounding machine in the production of the polyamide moulding material and need not be premixed.
In an especially preferred embodiment, the at least one amorphous polymer (d) is a mixture of an amorphous polyamide with a polyphenylene ether.
Polyphenylene ethers can be added either alone or as a blend with another pol-ymer to a compounding machine for producing the polyamide moulding material in accordance with the invention. In a preferred variant, the blend is a mixture with a polyamide. The polyamide of the blend is a semi-crystalline polyamide in an especially preferred manner, and more preferably of the same type as the component (a) of the polyamide moulding material in accordance with the in-vention.
The expression "mixtures" in connection with the component (d) means that in such a case two or more amorphous polymers (d) are contained in the polyam-ide moulding material in accordance with the invention. They can be added sep-arately to a compounding machine in the production of the polyamide moulding material and need not be premixed.
In an especially preferred embodiment, the at least one amorphous polymer (d) is a mixture of an amorphous polyamide with a polyphenylene ether.
Polyphenylene ethers can be added either alone or as a blend with another pol-ymer to a compounding machine for producing the polyamide moulding material in accordance with the invention. In a preferred variant, the blend is a mixture with a polyamide. The polyamide of the blend is a semi-crystalline polyamide in an especially preferred manner, and more preferably of the same type as the component (a) of the polyamide moulding material in accordance with the in-vention.
- 8 -Furthermore, the at least one amorphous polymer (d) has a glass transition temperature according to ISO 11357 of preferably 50 C to 280 C, especially preferably 60 C to 250 C, and more preferably 75 C to 220 C.
The at least one amorphous polymer (d) is preferably contained in the polyam-ide moulding material with 5 to 27% by weight, especially preferably 8 to 20%
by weight, and more preferably 7 to 17% by weight.
If the at least one amorphous polymer (d) comprises polyphenylene ether, the polyamide moulding material preferably contains 5 to 9% by weight of polyphe-nylene ether. The polyamide moulding material is free from polyphenylene ether in other preferred embodiments.
In a further preferred embodiment, the polyamide moulding material in accord-ance with the invention contains carbon black (e) in a fraction of 1 to 15% by weight, especially preferably 2 to 12% by weight, and more preferably 3 to 8%
by weight. Preferred carbon blacks are selected from commercially available trade products such as Ketjenblack , Ensaco , BASIONICS VS03, BASIONICS
LQ01, Vulcan P, Vulcan XC-72, Black Pearls 2000, etc. It is possible to use one single type of carbon black, or it is also possible to use mixtures of two or more types of carbon black.
The polyamide moulding material in accordance with the invention contains in a preferred embodiment at least one further additive and/or at least one further addition agent (f) selected from the group consisting of UV absorbers, UV
stabi-lisers, heat stabilisers, hydrolysis stabilisers, cross-linking activation agents, cross-linking agents, flame retardants, colouring agents, adhesion-promoting agents, compatibilizers, lubricants, glass fibres, auxiliary lubricants and mould release agents, inorganic pigments, organic pigments, IR absorbers, antistatic agents, anti-blocking agents, nucleation agents, crystallisation accelerants, crystallisation retarders, chain-lengthening additives, optical brighteners, photo-
The at least one amorphous polymer (d) is preferably contained in the polyam-ide moulding material with 5 to 27% by weight, especially preferably 8 to 20%
by weight, and more preferably 7 to 17% by weight.
If the at least one amorphous polymer (d) comprises polyphenylene ether, the polyamide moulding material preferably contains 5 to 9% by weight of polyphe-nylene ether. The polyamide moulding material is free from polyphenylene ether in other preferred embodiments.
In a further preferred embodiment, the polyamide moulding material in accord-ance with the invention contains carbon black (e) in a fraction of 1 to 15% by weight, especially preferably 2 to 12% by weight, and more preferably 3 to 8%
by weight. Preferred carbon blacks are selected from commercially available trade products such as Ketjenblack , Ensaco , BASIONICS VS03, BASIONICS
LQ01, Vulcan P, Vulcan XC-72, Black Pearls 2000, etc. It is possible to use one single type of carbon black, or it is also possible to use mixtures of two or more types of carbon black.
The polyamide moulding material in accordance with the invention contains in a preferred embodiment at least one further additive and/or at least one further addition agent (f) selected from the group consisting of UV absorbers, UV
stabi-lisers, heat stabilisers, hydrolysis stabilisers, cross-linking activation agents, cross-linking agents, flame retardants, colouring agents, adhesion-promoting agents, compatibilizers, lubricants, glass fibres, auxiliary lubricants and mould release agents, inorganic pigments, organic pigments, IR absorbers, antistatic agents, anti-blocking agents, nucleation agents, crystallisation accelerants, crystallisation retarders, chain-lengthening additives, optical brighteners, photo-
- 9 -chromic additives, impact modifiers, wherein maleic-anhydride-modified olefin copolymers and/or mixtures thereof are preferred as impact modifiers.
Examples for preferred impact modifiers are the following ones that are com-mercially available:
= TAFMER MC201: g-MAH (-0.6 /0) blend of 67% EP copolymer (20 mo10/0 propylene) + 33% EB copolymer (15 mol-% butene-1); Mitsui Chemicals, Japan.
= TAFMER MH5010: g-MAH (-0.6 %) ethylene butylene copolymer; Mitsui.
= TAFMER MH7010: g-MAH (-0.7 %) ethylene butylene copolymer; Mitsui.
= TAFMER MH7020: g-MAH (-0.7 /0) EP copolymer, Mitsui.
= EXXELOR VA1801: g-MAH (-0.7 0/0) EP copolymer; Exxon Mobile Chemi-cal, US.
= EXXELOR VA1803: g-MAH (0.5-0.9 /0) EP copolymer, amorphous, Exxon.
= EXXELOR VA1810: g-MAH (-0.5 0/0) EP copolymer, Exxon.
= EXXELOR MDEX 94-1 1: g-MAH (0.7 /0) EPDM, Exxon.
= FUSABOND MN493D: g-MAH (-0.5 0/0) ethylene octene copolymer, DuPont, US.
= FUSABOND A EB560D (g-MAH) ethylene-n-butyl acrylate copolymer, DuPont.
= ELVALOY, DuPont.
= Lotader AX 8840, Arkema, FR.
= Bondyram, IL.
The polyamide moulding material is free from lubricants and/or free from com-patibilizers in preferred embodiments.
The further additives and/or addition agents (f) are contained in the polyamide moulding material preferably with 0.1 to 15% by weight, especially preferably with 0.2 to 10% by weight, and more preferably with 0.25 to 5% by weight.
Examples for preferred impact modifiers are the following ones that are com-mercially available:
= TAFMER MC201: g-MAH (-0.6 /0) blend of 67% EP copolymer (20 mo10/0 propylene) + 33% EB copolymer (15 mol-% butene-1); Mitsui Chemicals, Japan.
= TAFMER MH5010: g-MAH (-0.6 %) ethylene butylene copolymer; Mitsui.
= TAFMER MH7010: g-MAH (-0.7 %) ethylene butylene copolymer; Mitsui.
= TAFMER MH7020: g-MAH (-0.7 /0) EP copolymer, Mitsui.
= EXXELOR VA1801: g-MAH (-0.7 0/0) EP copolymer; Exxon Mobile Chemi-cal, US.
= EXXELOR VA1803: g-MAH (0.5-0.9 /0) EP copolymer, amorphous, Exxon.
= EXXELOR VA1810: g-MAH (-0.5 0/0) EP copolymer, Exxon.
= EXXELOR MDEX 94-1 1: g-MAH (0.7 /0) EPDM, Exxon.
= FUSABOND MN493D: g-MAH (-0.5 0/0) ethylene octene copolymer, DuPont, US.
= FUSABOND A EB560D (g-MAH) ethylene-n-butyl acrylate copolymer, DuPont.
= ELVALOY, DuPont.
= Lotader AX 8840, Arkema, FR.
= Bondyram, IL.
The polyamide moulding material is free from lubricants and/or free from com-patibilizers in preferred embodiments.
The further additives and/or addition agents (f) are contained in the polyamide moulding material preferably with 0.1 to 15% by weight, especially preferably with 0.2 to 10% by weight, and more preferably with 0.25 to 5% by weight.
- 10 -A plastic moulding material in accordance with the invention preferably has a specific surface resistance of 1*10-1 to 1*104, especially preferably 1 to 1*103, and more preferably 1*101 to 9*102 ohms. The specific volume resistance of a plastic moulding material in accordance with the invention is preferably 1*10-to 1*103, especially preferably 1*104 to 1*102, more preferably 1 to 5*101 ohm*m.
Preferred gloss values are at least 80, and especially preferably at least 90, measured according to the method disclosed below. The inventors were sur-prised to find that an important influential factor in the achievement of such high gloss values is the addition of an amorphous polymer (d) with a glass tran-sition temperature of at least 45 C to a semi-crystalline polyamide.
Preferred mechanical properties relate to minimum values for impact strength (at least 28 kJ/m2), notch impact strength (at least 4.8 kJ/m2), elongation at tear (at least 1.4 %), tensile modulus (at least 5000 MPa) and tear strength (at least 70 MPa).
An especially preferred moulding material has the following composition:
(a) 32 to 58% by weight of at least one semi-crystalline aliphatic polyam-ide, especially PA 66 or PA 612;
(b) 4 to 17% by weight of carbon fibres with a fibre diameter in the range of 2 to 10 pm;
(c) 30 to 45% by weight of at least one particulate mineral or saline filler;
(d) 8 to 20% by weight of at least one amorphous polymer with a glass transition temperature of at least 45 C determined according to ISO
11357;
(e) 0% by weight of carbon black;
(f) 0 to 5% by weight of at least one further additive and/or addition agent, wherein the components (a) to (f) add up in total to 100% by weight.
,
Preferred gloss values are at least 80, and especially preferably at least 90, measured according to the method disclosed below. The inventors were sur-prised to find that an important influential factor in the achievement of such high gloss values is the addition of an amorphous polymer (d) with a glass tran-sition temperature of at least 45 C to a semi-crystalline polyamide.
Preferred mechanical properties relate to minimum values for impact strength (at least 28 kJ/m2), notch impact strength (at least 4.8 kJ/m2), elongation at tear (at least 1.4 %), tensile modulus (at least 5000 MPa) and tear strength (at least 70 MPa).
An especially preferred moulding material has the following composition:
(a) 32 to 58% by weight of at least one semi-crystalline aliphatic polyam-ide, especially PA 66 or PA 612;
(b) 4 to 17% by weight of carbon fibres with a fibre diameter in the range of 2 to 10 pm;
(c) 30 to 45% by weight of at least one particulate mineral or saline filler;
(d) 8 to 20% by weight of at least one amorphous polymer with a glass transition temperature of at least 45 C determined according to ISO
11357;
(e) 0% by weight of carbon black;
(f) 0 to 5% by weight of at least one further additive and/or addition agent, wherein the components (a) to (f) add up in total to 100% by weight.
,
-11 -Polyamide moulded bodies are also provided in accordance with the invention, which can be produced at least in sections from a polyamide moulding material as described above, e.g. by injection moulding. These polyamide moulded bod-ies are preferably provided in form of components which require electrical con-ductivity, for interior and exterior parts in the automotive sector and in the re-gion of other means of transport, preferably for filler cap covers, in the electric and electronic sector, especially for parts of the housing or housing component for portable electronic devices, domestic appliances, domestic machines, devic-es and apparatuses for telecommunications and consumer electronics, prefera-bly mobile phones, interior and exterior parts with preferably supporting me-chanical function with electrical conductivity in the areas of electricity, furniture, sports, mechanical engineering, sanitation and hygiene, medicine, energy and drive technology.
The invention further relates to the use of particulate mineral or saline fillers for reducing the specific surface resistance and/or the specific volume resistance of carbon-fibre-containing polyamide moulding materials with a carbon fibre diam-eter in the range of 2 to 10 pm.
The present invention will be explained below in closer detail by reference to the following examples which illustrate the invention but do not limit the scope of the invention.
The materials mentioned in Table 1 were used in the examples and comparison examples.
The invention further relates to the use of particulate mineral or saline fillers for reducing the specific surface resistance and/or the specific volume resistance of carbon-fibre-containing polyamide moulding materials with a carbon fibre diam-eter in the range of 2 to 10 pm.
The present invention will be explained below in closer detail by reference to the following examples which illustrate the invention but do not limit the scope of the invention.
The materials mentioned in Table 1 were used in the examples and comparison examples.
- 12 -Table 1: Employed materials.
Substance Trade name Manufacturer Rel. vis-H20 con-cosity tent [ /0 by weight]
PA 66 A RADIPOL A40 Radici (IT) 2.503a) 0.03 PA 66 B RADIPOL A45 Radici (IT) 2.736a) 0.025 PA 612 Grivory XE 1291 EMS-GRIVORY 1.820a) 0.02 (CH) PA 6I/6T (2:1) GRIVORY G21 EMS-GRIVORY 1.530b) 0.03 (amorphous, Tg (CH) =125 Cc)) Calcium carbonate Millicarb Omya (DE) (mean particle size d50, 3 pm) Carbon fibre CF TENAX E-HT Toho Tenax (DE) Stabiliser Irganox 1098 BASF (CH) Carbon black Ketjenblack EC- Akzo Nobel (NL) Impact modifier 1 Bondyram 7103 Polyram (IL) Impact modifier 2 Bondyram 7107 Polyram (IL) Impact modifier 3 Bondyram Polyram (IL) Polyphenylene Bondyram 6008 Polyram (IL) ether (Blend of 49% by (amorphous, Tg weight of PPE, =2000C) 49% by weight of PA 66 and 2% by weight of MAH) a) Determined according to ISO 307 (1.0 g of polyamide dissolved in 100 mL of H2504), calculation of relative viscosity (RV) according to RV = tit based on section 11 of the standard.
b) Determined according to ISO 307 (0.5 g of polyamide dissolved in 100 mL of m-cresol), calculation of relative viscosity (RV) according to RV = tit based on section 11 of the standard.
c) Determined according to ISO 11357.
=
Substance Trade name Manufacturer Rel. vis-H20 con-cosity tent [ /0 by weight]
PA 66 A RADIPOL A40 Radici (IT) 2.503a) 0.03 PA 66 B RADIPOL A45 Radici (IT) 2.736a) 0.025 PA 612 Grivory XE 1291 EMS-GRIVORY 1.820a) 0.02 (CH) PA 6I/6T (2:1) GRIVORY G21 EMS-GRIVORY 1.530b) 0.03 (amorphous, Tg (CH) =125 Cc)) Calcium carbonate Millicarb Omya (DE) (mean particle size d50, 3 pm) Carbon fibre CF TENAX E-HT Toho Tenax (DE) Stabiliser Irganox 1098 BASF (CH) Carbon black Ketjenblack EC- Akzo Nobel (NL) Impact modifier 1 Bondyram 7103 Polyram (IL) Impact modifier 2 Bondyram 7107 Polyram (IL) Impact modifier 3 Bondyram Polyram (IL) Polyphenylene Bondyram 6008 Polyram (IL) ether (Blend of 49% by (amorphous, Tg weight of PPE, =2000C) 49% by weight of PA 66 and 2% by weight of MAH) a) Determined according to ISO 307 (1.0 g of polyamide dissolved in 100 mL of H2504), calculation of relative viscosity (RV) according to RV = tit based on section 11 of the standard.
b) Determined according to ISO 307 (0.5 g of polyamide dissolved in 100 mL of m-cresol), calculation of relative viscosity (RV) according to RV = tit based on section 11 of the standard.
c) Determined according to ISO 11357.
=
- 13 -Compounding In general, the components are mixed in the polymer melt (compounded) on conventional compounding machines such as single-shaft or double-shaft ex-truders or screw mixers for the production of the plastic moulding material.
The components are dosed individually to the feed or supplied in form of a dryblend.
If addition agents (additives) are used, they can be introduced directly or in form of a master batch. In the case of a dryblend production, the dried polymer granulates and the additives are mixed. The mixing can occur under a dried protective gas for avoiding the absorption of humidity.
Compounding is carried out at set extruder cylinder temperatures of 230 C to 350 C for example. A vacuum can be applied before the nozzle or it can be at-mospherically degassed. The melt is discharged in stranded shape to a water bath and granulated. Underwater granulation or hot die-face cutting is prefera-bly used for granulation. The plastic moulding material thus preferably obtained in granular form is subsequently dried and can subsequently be further pro-cessed into shaped bodies.
The moulding materials for the examples B1 to B8 in accordance with the inven-tion and for the comparative examples VB1 to VB6 were produced on a two-shaft extruder of "Werner und Pfleiderer" Co. The mass fractions of the starting materials stated in Table 2 in percent by weight (% by weight) relating to 100%
by weight of the entire moulding material were compounded in the two-shaft extruder. Sample bodies were injection-moulded from the obtained granulate, from which the properties stated in Table 3 were determined.
Standards for determining the mechanical data and the electrical con-ductivity properties The mechanical data and conductivity properties stated in Table 3 (wherein the latter is expressed by the electric resistance which acts inversely proportional to the conductivity) were determined according to the following standards:
The components are dosed individually to the feed or supplied in form of a dryblend.
If addition agents (additives) are used, they can be introduced directly or in form of a master batch. In the case of a dryblend production, the dried polymer granulates and the additives are mixed. The mixing can occur under a dried protective gas for avoiding the absorption of humidity.
Compounding is carried out at set extruder cylinder temperatures of 230 C to 350 C for example. A vacuum can be applied before the nozzle or it can be at-mospherically degassed. The melt is discharged in stranded shape to a water bath and granulated. Underwater granulation or hot die-face cutting is prefera-bly used for granulation. The plastic moulding material thus preferably obtained in granular form is subsequently dried and can subsequently be further pro-cessed into shaped bodies.
The moulding materials for the examples B1 to B8 in accordance with the inven-tion and for the comparative examples VB1 to VB6 were produced on a two-shaft extruder of "Werner und Pfleiderer" Co. The mass fractions of the starting materials stated in Table 2 in percent by weight (% by weight) relating to 100%
by weight of the entire moulding material were compounded in the two-shaft extruder. Sample bodies were injection-moulded from the obtained granulate, from which the properties stated in Table 3 were determined.
Standards for determining the mechanical data and the electrical con-ductivity properties The mechanical data and conductivity properties stated in Table 3 (wherein the latter is expressed by the electric resistance which acts inversely proportional to the conductivity) were determined according to the following standards:
- 14 -Tensile modulus:
ISO 527 with a tensile velocity of 1 mm/min ISO tension rod, standard: ISO 3167, type A, 170 x 20/10 x 4 mm, tempera-ture 23 C.
Tear strength and elongation at tear:
ISO 527 with a tensile velocity of 5 mm/min ISO tension rod, standard: ISO 3167, type A, 170 x 20/10 x 4 mm, tempera-ture 23 C.
Charpy impact strength and Charpy notched bar impact strength:
ISO 179-2/1eU (Charpy impact strength) ISO tension rod, standard: ISO 179-1, type 1, 80 x 10 x 4 mm, temperature 23 C.
Specific (electrical) resistivity:
(also known as specific volume resistance, in [ohm*rn]) Plates 100*100*2 mm, contact with conductive silver Specific (electrical) surface resistance:
(also known as CI square due to electrode arrangement, in [ohm]) Plates 100*100*2 mm, contact with conductive silver Gloss values:
Gloss was determined on plates of the dimension 80x80x1 mm with a device of type Minolta Multi Gloss 268 under an angle of 85 and at a temperature of 23 C according to ISO 2813. The gloss value is stated in dimensionless gloss units (GU, gloss units).
, ,
ISO 527 with a tensile velocity of 1 mm/min ISO tension rod, standard: ISO 3167, type A, 170 x 20/10 x 4 mm, tempera-ture 23 C.
Tear strength and elongation at tear:
ISO 527 with a tensile velocity of 5 mm/min ISO tension rod, standard: ISO 3167, type A, 170 x 20/10 x 4 mm, tempera-ture 23 C.
Charpy impact strength and Charpy notched bar impact strength:
ISO 179-2/1eU (Charpy impact strength) ISO tension rod, standard: ISO 179-1, type 1, 80 x 10 x 4 mm, temperature 23 C.
Specific (electrical) resistivity:
(also known as specific volume resistance, in [ohm*rn]) Plates 100*100*2 mm, contact with conductive silver Specific (electrical) surface resistance:
(also known as CI square due to electrode arrangement, in [ohm]) Plates 100*100*2 mm, contact with conductive silver Gloss values:
Gloss was determined on plates of the dimension 80x80x1 mm with a device of type Minolta Multi Gloss 268 under an angle of 85 and at a temperature of 23 C according to ISO 2813. The gloss value is stated in dimensionless gloss units (GU, gloss units).
, ,
- 15 -Tests The compositions of the moulding materials of the performed tests (B = exam-ples in accordance with the invention, and VB = comparative examples) are shown in the following Table 2.
The results of the measurements are summarised in Table 3.
Table 2: Compositions (in percent by weight).
Examples B1 B2 B3 B4 B5 B6 PA 66 A - - 37.25 26.07 31.0 31.0 31.0 PA 66 B - 37.25 - - - --PA 612 35.75 - - - - --PA 61/6T 14.0 12.5 12.5 8.75 10.4 10.4 10.4 (2:1) Calcium 35.0 35.0 35.0 35.0 40.0 40.0 40.0 carbonate Carbon fibre 15.0 15.0 15.0 15.0 5.0 5.0 5.0 Stabiliser 0.25 0.25 0.25 0.25 0.25 0.25 0.25 Carbon black - - - - 3.0 3.0 3.0 Impact - - - - 10.35 --modifier 1 Impact - - - - - 10.35 -modifier 2 Impact - - - - - -10.35 modifier 3 Polyphenylene - - - 14.93 - --ether blend (7.32 PPE) Examples B8 VB1 VB2 VB3 VB4 VBS VB6 PA 66 A 34.82 31.0 - 37.3 63.5 52.275 44.75 PA 6I/6T - 10.4 34.82 12.52 21.25 17.545 -(2:1) Calcium 35.0 40.0 35.0 35.0 - -35.0 carbonate Carbon fibre 15.0 - 15.0 - 15.0 15.0 15.0
The results of the measurements are summarised in Table 3.
Table 2: Compositions (in percent by weight).
Examples B1 B2 B3 B4 B5 B6 PA 66 A - - 37.25 26.07 31.0 31.0 31.0 PA 66 B - 37.25 - - - --PA 612 35.75 - - - - --PA 61/6T 14.0 12.5 12.5 8.75 10.4 10.4 10.4 (2:1) Calcium 35.0 35.0 35.0 35.0 40.0 40.0 40.0 carbonate Carbon fibre 15.0 15.0 15.0 15.0 5.0 5.0 5.0 Stabiliser 0.25 0.25 0.25 0.25 0.25 0.25 0.25 Carbon black - - - - 3.0 3.0 3.0 Impact - - - - 10.35 --modifier 1 Impact - - - - - 10.35 -modifier 2 Impact - - - - - -10.35 modifier 3 Polyphenylene - - - 14.93 - --ether blend (7.32 PPE) Examples B8 VB1 VB2 VB3 VB4 VBS VB6 PA 66 A 34.82 31.0 - 37.3 63.5 52.275 44.75 PA 6I/6T - 10.4 34.82 12.52 21.25 17.545 -(2:1) Calcium 35.0 40.0 35.0 35.0 - -35.0 carbonate Carbon fibre 15.0 - 15.0 - 15.0 15.0 15.0
- 16 -Stabiliser 0.25 0.25 0.25 0.25 0.25 0.25 0.25 Carbon black - 8.0 - - - - -Impact - 10.35 - - - - 5 modifier 1 Polyphenylene 14.93 - 14.93 14.93 - 14.93 -ether blend (7.32 (7.32 (7.32 (7.32 PPE) PPE) PPE) PPE)
- 17 -Table 3: Results of the measurements.
Examples B1 B2 B3 B4 B5 B6 B7 Specific volume 3.9*101 2.7 4.5 4.0 1.8*101 2.3*101 2.7*101 resistance [ohm*m]
Specific surface 7.5*102 1.2*102 1.8*102 1.6*102 2.7*102 3.8*102 6.6*102 resistance [ohm]
Gloss 85 93.3 94.5 84.2 93.5 89.7 90.9 80.9 Impact strength 39.7 47.9 50.4 41.6 39.4 36.5 29.2 23 C, dry [kJ/m2]
Notch impact 5.1 6.5 6.5 6.6 7.0 6.9 5.0 strength, 23 C, dry [kJ/m2]
Elongation at 1.6 1.8 1.9 1.5 3.2 3.3 2.4 tear [0/0]
Tensile modulus 19500 18200 18600 18500 6000 5800 [MPa]
Tear strength 204 205 210 197 75 74 84 [MPa]
Examples B8 VB1 VB2 VB3 VB4 VB5 VB6 Specific volume 2.8 2.5*101 1.1 8.3*108 1.6*104 4.1*104 9.5 resistance *10-1 [ohm*m]
Specific surface 9.2*101 4.2*102 5.5*101 3.5*1010 1.3*105 2.4*106 5.0*101 resistance [ohm]
Gloss 85 92.6 48.3 79.8 90.7 79.1 80.7 67.5 Impact strength 38.9 5 23.6 48.1 38.0 38.9 49.5 23 C, dry [kJ/m2]
Notch impact 6.4 1.1 5.1 4.6 5.1 4.7 6.4 strength, 23 C, dry [kJ/m2]
Elongation at 1.5 0.3 1.3 1.6 3.9 4.1 1.0 tear [ /0]
Tensile modulus 18900 250 19000 4400 11600 11100 [MPa]
Tear strength 195 17 187 62 170 160 [MPa]
Examples B1 B2 B3 B4 B5 B6 B7 Specific volume 3.9*101 2.7 4.5 4.0 1.8*101 2.3*101 2.7*101 resistance [ohm*m]
Specific surface 7.5*102 1.2*102 1.8*102 1.6*102 2.7*102 3.8*102 6.6*102 resistance [ohm]
Gloss 85 93.3 94.5 84.2 93.5 89.7 90.9 80.9 Impact strength 39.7 47.9 50.4 41.6 39.4 36.5 29.2 23 C, dry [kJ/m2]
Notch impact 5.1 6.5 6.5 6.6 7.0 6.9 5.0 strength, 23 C, dry [kJ/m2]
Elongation at 1.6 1.8 1.9 1.5 3.2 3.3 2.4 tear [0/0]
Tensile modulus 19500 18200 18600 18500 6000 5800 [MPa]
Tear strength 204 205 210 197 75 74 84 [MPa]
Examples B8 VB1 VB2 VB3 VB4 VB5 VB6 Specific volume 2.8 2.5*101 1.1 8.3*108 1.6*104 4.1*104 9.5 resistance *10-1 [ohm*m]
Specific surface 9.2*101 4.2*102 5.5*101 3.5*1010 1.3*105 2.4*106 5.0*101 resistance [ohm]
Gloss 85 92.6 48.3 79.8 90.7 79.1 80.7 67.5 Impact strength 38.9 5 23.6 48.1 38.0 38.9 49.5 23 C, dry [kJ/m2]
Notch impact 6.4 1.1 5.1 4.6 5.1 4.7 6.4 strength, 23 C, dry [kJ/m2]
Elongation at 1.5 0.3 1.3 1.6 3.9 4.1 1.0 tear [ /0]
Tensile modulus 18900 250 19000 4400 11600 11100 [MPa]
Tear strength 195 17 187 62 170 160 [MPa]
- 18 -The examples of the invention show that polyamide moulding materials are ob-tained by a combination of the features in accordance with the invention which, in addition to good mechanical properties, surprisingly also show very good electrical conductivity and very good surface properties. Gloss is used as a measure for the surface properties. Comparative example VB1, which merely contains carbon black instead of the carbon fibres in accordance with the inven-tion, shows a very low gloss value and very bad mechanical properties. The gloss and the impact strength are impaired by leaving out the semi-crystalline component as in the comparative example VB2. Comparative example VB6 shows that the gloss will deteriorate distinctly if no amorphous polymer is con-tained in the moulding material. The comparative examples VB3 to VB5 demon-strate impressively that both the carbon fibre and also the particulate filler are necessary in order to achieve very good electrical conductivity, or that this is not achieved when one of these two components is missing. The measured spe-cific resistances, which act inversely to the electrical conductivity, are higher by a factor of 103 to 108 in VB3, VB4 and VB5 than in the examples in accordance with the invention. Example B4 is an example for a preferred embodiment which contains both an amorphous polyamide and also a polyphenylene ether, i.e. in which the at least one amorphous polymer (d) represents a mixture of an amorphous polyamide with a polyphenylene ether. The examples B5 to B7 show that the carbon fibre fraction can be reduced when carbon black is added to the moulding material. Partly better conductivities (lower resistances) are obtained on the other hand by 5% by weight of carbon fibres and 3% by weight of car-bon black than by 8% by weight of carbon black (in comparison with VB1). The example B8 shows that very good gloss values are also obtained when the moulding material, as an amorphous polymer (d), contains an amorphous non-polyamide such as a polyphenylene ether instead of an amorphous polyamide.
The present invention can thus provide advantageous polyamide moulding ma-terials which in a manner unexpected to the person skilled in the art simultane-,
The present invention can thus provide advantageous polyamide moulding ma-terials which in a manner unexpected to the person skilled in the art simultane-,
- 19 -ously fulfil the requirements of high electrical conductivity, smooth surface (high gloss) and very good mechanical properties. Shaped bodies made from such moulding materials are of high quality, have a pleasant appearance and are also highly suitable among other things for electrostatic powder coating and electro-dip painting (KTL process). It was not obvious to a person skilled in the art with respect to the prior art that this can be achieved in accordance with the inven-tion by carbon fibres in the conventional diameter range (instead of carbon nanotubes) and preferably also without a polyphenylene ether component.
Claims (16)
1. A polyamide moulding material, having the following composition:
(a) 20 to 85% by weight of at least one semi-crystalline polyamide;
(b) 4 to 18% by weight of carbon fibres with a fibre diameter in the range of 2 to 10 µm;
(c) 10 to 60% by weight of at least one particulate mineral or saline fill-er;
(d) 3 to 30% by weight of at least one amorphous polymer with a glass transition temperature of at least 45°C determined according to ISO
11357;
(e) 0 to 20% by weight of carbon black;
(f) 0 to 20% by weight of at least one further additive and/or addition agent;
wherein the components (a) to (f) add up in total to 100% by weight.
(a) 20 to 85% by weight of at least one semi-crystalline polyamide;
(b) 4 to 18% by weight of carbon fibres with a fibre diameter in the range of 2 to 10 µm;
(c) 10 to 60% by weight of at least one particulate mineral or saline fill-er;
(d) 3 to 30% by weight of at least one amorphous polymer with a glass transition temperature of at least 45°C determined according to ISO
11357;
(e) 0 to 20% by weight of carbon black;
(f) 0 to 20% by weight of at least one further additive and/or addition agent;
wherein the components (a) to (f) add up in total to 100% by weight.
2. A polyamide moulding material according to claim 1, characterized in that the semi-crystalline polyamide (a) is an aliphatic or a semi-aromatic polyamide.
3. A polyamide moulding material according to claim 1 or 2, characterized in that the semi-crystalline polyamide (a) is selected from the group con-sisting of PA 46, PA 6, PA 66, PA 11, PA 12, PA 610, PA 1212, PA 1010, PA
10/11, PA 10/12, PA 11/12, PA 6/10, PA 6/12, PA 6/9, PA 8/10, PA 612, PA 614, PA 66/6, PA 4T/4I, PA 4T/6I, PA 5T/5I, PA 6T/6I, PA 6T/6I/6, PA
6T/66, PA 6T/610, PA 10T/106, PA 6T/612, PA 6T/10T, PA 6T/10I, PA 9T, PA 10T, PA 12T, PA 10T/10I, PA10T/12, PA10T/11, PA 6T/9T, PA 6T/12T, PA 6T/10T/61, PA 6T/6I/6, PA 6T/6I/12, PA 10T/612, PA 10T/610, and/or mixtures, blends or alloys of said polyamides, wherein PA 66 and PA 612 are preferred.
10/11, PA 10/12, PA 11/12, PA 6/10, PA 6/12, PA 6/9, PA 8/10, PA 612, PA 614, PA 66/6, PA 4T/4I, PA 4T/6I, PA 5T/5I, PA 6T/6I, PA 6T/6I/6, PA
6T/66, PA 6T/610, PA 10T/106, PA 6T/612, PA 6T/10T, PA 6T/10I, PA 9T, PA 10T, PA 12T, PA 10T/10I, PA10T/12, PA10T/11, PA 6T/9T, PA 6T/12T, PA 6T/10T/61, PA 6T/6I/6, PA 6T/6I/12, PA 10T/612, PA 10T/610, and/or mixtures, blends or alloys of said polyamides, wherein PA 66 and PA 612 are preferred.
4. A polyamide moulding material according to one of the preceding claims, characterized in that the at least one semi-crystalline polyamide (a) is contained in the polyamide moulding material with 25 to 50% by weight, preferably 27 to 45% by weight, and more preferably 30 to 40% by weight.
5. A polyamide moulding material according to one of the preceding claims, characterized in that the carbon fibres (b) are contained in the polyam-ide moulding material with 5 to 16% by weight.
6. A polyamide moulding material according to one of the preceding claims, characterized in that the particulate mineral or saline filler (c) is selected from the group consisting of calcium carbonate, magnesium carbonate, do-lomite, calcium hydroxide, magnesium hydroxide, calcium sulphate, bari-um sulphate, barite, calcium silicates, aluminium silicates, kaolin, chalk, mica, layered silicates, talcum, clay, and/or mixtures of said fillers, where-in calcium carbonate is preferred.
7. A polyamide moulding material according to one of the preceding claims, characterized in that the at least one particulate mineral or saline filler (c) is contained in the polyamide moulding material with 15 to 55% by weight, preferably 20 to 50% by weight, and more preferably 35 to 45%
by weight.
by weight.
8. A polyamide moulding material according to one of the preceding claims, characterized in that the at least one amorphous polymer (d) is selected from the group consisting of PA 61, PA 101, copolyamides 61/6T with a mol ratio of isophthalic acid to terephthalic acid of between 1:0 and 3:2, copol-yamides 101/10T with a mol ratio of isophthalic acid to terephthalic acid of between 1:0 and 3:2, polyphenylene ethers, especially poly(2,6-diethyl-1,4-phenylene) ether, poly(2-methyl-6-ethyl-1,4-phenylene) ether, poly(2-methyl-6-propyl-1,4-phenylene) ether, poly(2,6-dipropyl-1,4-phenylene) ether, poly(2-ethyl-6-propyl-1,4-phenylene) ether, polyphenylene ether copolymers which contain 2,3,6-trimethyl phenol, grafted variants of the aforementioned polyphenylene ethers, further mixtures of the aforemen-tioned polyphenylene ethers, and/or mixtures of the aforementioned amorphous polymers, wherein a copolyamide 6I/6T with a mol ratio of isophthalic acid to terephthalic acid of 2:1 is preferred.
9. A polyamide moulding material according to one of the preceding claims, characterized in that the at least one amorphous polymer (d) has a glass transition temperature determined according to ISO 11357 of 50°C
to 280°C, preferably 60°C to 250°C, and more preferably 75°C to 220°C.
to 280°C, preferably 60°C to 250°C, and more preferably 75°C to 220°C.
10. A polyamide moulding material according to one of the preceding claims, characterized in that the at least one amorphous polymer (d) is con-tained in the polyamide moulding material with 5 to 27% by weight, pref-erably 8 to 20% by weight, and more preferably 7 to 17% by weight.
11. A polyamide moulding material according to one of the preceding claims, characterized in that the at least one amorphous polymer (d) comprises polyphenylene ether, wherein the polyamide moulding material contains 5 to 9% by weight of polyphenylene ether.
12. A polyamide moulding material according to one of the preceding claims, characterized in that the carbon black (e) is contained in the polyamide moulding material with 1 to 15% by weight, preferably 2 to 12% by weight, and more preferably 3 to 8% by weight.
13. A polyamide moulding material according to one of the preceding claims, characterized in that the at least one further additive and/or the at least one further addition agent (f) is selected from the group consisting of UV
absorbers, UV stabilisers, heat stabilisers, hydrolysis stabilisers, cross-linking activation agents, cross-linking agents, flame retardants, colouring agents, adhesion-promoting agents, compatibilizers, lubricants, glass fi-bres, auxiliary lubricants and mould release agents, inorganic pigments, organic pigments, IR absorbers, antistatic agents, anti-blocking agents, nucleation agents, crystallisation accelerants, crystallisation retarders, chain-lengthening additives, optical brighteners, photochromic additives, impact modifiers, wherein maleic-anhydride-modified olefin copolymers and/or mixtures thereof are preferred as impact modifiers.
absorbers, UV stabilisers, heat stabilisers, hydrolysis stabilisers, cross-linking activation agents, cross-linking agents, flame retardants, colouring agents, adhesion-promoting agents, compatibilizers, lubricants, glass fi-bres, auxiliary lubricants and mould release agents, inorganic pigments, organic pigments, IR absorbers, antistatic agents, anti-blocking agents, nucleation agents, crystallisation accelerants, crystallisation retarders, chain-lengthening additives, optical brighteners, photochromic additives, impact modifiers, wherein maleic-anhydride-modified olefin copolymers and/or mixtures thereof are preferred as impact modifiers.
14. A polyamide moulding material according to one of the preceding claims, characterized in that the further additive and/or the further addition agent (f) is contained in the polyamide moulding material with 0.1 to 15%
by weight, preferably 0.2 to 10% by weight, and more preferably 0.25 to 5% by weight.
by weight, preferably 0.2 to 10% by weight, and more preferably 0.25 to 5% by weight.
15. A polyamide moulded body which consists at least in sections of a polyam-ide moulding material according to one of the claims 1 to 14, preferably provided in form of components which require electrical conductivity, for interior and exterior parts in the automotive sector and in the region of other means of transport, preferably for filler cap covers, in the electric and electronic sector, especially for parts of a housing or housing compo-nent for portable electronic devices, domestic appliances, domestic ma-chines, devices and apparatuses for telecommunications and consumer electronics, preferably mobile phones, interior and exterior parts with pref-erably supporting mechanical function with electrical conductivity in the ar-eas of electricity, furniture, sports, mechanical engineering, sanitation and hygiene, medicine, energy and drive technology.
16. The use of particulate mineral or saline fillers for reducing the specific sur-face resistance and/or the specific volume resistance of carbon-fibre-containing polyamide moulding materials with a carbon-fibre diameter in the range of 2 to 10 µm.
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| CH5432014 | 2014-04-08 | ||
| CH00543/14 | 2014-04-08 | ||
| EP15155617.2A EP2930212B1 (en) | 2014-04-08 | 2015-02-18 | Electrically conductive polyamide moulding compositions |
| EP15155617.2 | 2015-02-18 |
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2015
- 2015-02-18 EP EP15155617.2A patent/EP2930212B1/en active Active
- 2015-03-13 TW TW104107997A patent/TWI660003B/en active
- 2015-03-13 CA CA2885137A patent/CA2885137C/en active Active
- 2015-04-02 KR KR1020150046663A patent/KR102276640B1/en active IP Right Grant
- 2015-04-07 US US14/680,608 patent/US20150287493A1/en not_active Abandoned
- 2015-04-07 JP JP2015078391A patent/JP6633835B2/en active Active
- 2015-04-07 CN CN201510161498.4A patent/CN104974515B/en active Active
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| KR102276640B1 (en) | 2021-07-13 |
| CA2885137C (en) | 2022-02-22 |
| TWI660003B (en) | 2019-05-21 |
| TW201602237A (en) | 2016-01-16 |
| US20150287493A1 (en) | 2015-10-08 |
| KR20150116781A (en) | 2015-10-16 |
| CN104974515A (en) | 2015-10-14 |
| EP2930212B1 (en) | 2019-04-10 |
| JP2015199959A (en) | 2015-11-12 |
| CN104974515B (en) | 2019-03-15 |
| EP2930212A1 (en) | 2015-10-14 |
| JP6633835B2 (en) | 2020-01-22 |
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